JP2017501906A - Furan-based polymer hydrocarbon fuel barrier structure - Google Patents

Abstract

A multilayer structure and an article comprising the multilayer structure are disclosed herein. The multilayer structure includes a hydrocarbon fuel permeation barrier layer comprising a furan-based polyester; a structural layer; and a tie layer disposed between the barrier layer and the structural layer to provide a permeation barrier for hydrocarbon fuel.

Description

This application claims the benefit of US Provisional Application No. 61 / 918,708, filed Dec. 20, 2013, which is hereby incorporated by reference in its entirety.

  The present invention relates generally to furan-based polyesters, particularly hydrocarbon fuel permeation barrier layers comprising furan-based polyesters and articles made therefrom for use in the storage or transport of hydrocarbon fuels.

  Several existing hydrocarbon barrier polymer technologies are now on the market, including liquid crystalline polymers, fluoropolymers (eg Tefzel®, ethylene tetrafluoroethylene copolymer (ETFE)) and polyethylene-co-vinyl alcohol (EVOH) Exists. Another hydrocarbon barrier technique is a laminar technique in which polyamide 6 or EVOH platelets are formed in an HDPE matrix and with on-line and off-line fluorination. EVOH when used as a continuous layer offers a combination of low cost and excellent performance and is therefore the most widely used polymer hydrocarbon barrier. However, EVOH with a low ethylene content (32% or less) has disadvantages such as brittleness and increased penetration at high water content due to the hydrophilic nature of the vinyl alcohol group. EVOH is typically used in multi-layer packaging, using HDPE as the outer substrate and EVOH as the intermediate barrier layer.

  Accordingly, there is a need for new polymers that provide a permeation barrier for hydrocarbon fuels.

In the first embodiment,
a. A hydrocarbon fuel permeation barrier layer comprising a furan-based polyester, wherein the furan-based polyester is:
i. 2,5-furandicarboxylic acid or a derivative thereof,
ii. C ₂ -C ₁₂ aliphatic diol or polyol, and iii. Optionally, at least one of polyalkylene ether glycol (PAEG), polyfunctional acid or polyfunctional hydroxyl acid;
A hydrocarbon fuel permeation barrier layer derived from
b. A first structural layer comprising at least one of a polyolefin, polyester, or polyamide;
c. A first tie layer disposed between the barrier layer and the first structural layer, the first tie layer comprising an ethylene-based copolymer;
A multilayer structure comprising
A multilayer structure is provided having a thickness in the range of 0.5 to 50% of the total thickness of the multilayer structure such that the hydrocarbon fuel permeation barrier layer provides a permeation barrier for hydrocarbon fuel.

  In the second embodiment, the multilayer structure further includes a second structural layer, wherein the barrier layer is disposed between the first tie layer and the second structural layer.

  In a third embodiment, the multilayer structure further includes a second tie layer, wherein the barrier layer is disposed between the first tie layer and the second tie layer, and the first tie layer comprises an ethylene-based copolymer. .

  In a fourth embodiment of the multilayer structure, the furan-based polyester is poly (trimethylene furandicarboxylate).

  In a fifth embodiment of the multilayer structure, the barrier layer further comprises poly (trimethylene furandicarboxylate) (PTF), such that the furan-based polyester is different from PTF, the furan-based polyester and PTF are A polymer blend comprising 0.1 to 99.9% by weight of PTF is formed relative to the total weight of the polymer blend composition comprising furan-based polyester and PTF.

  In a sixth embodiment of the multilayer structure, the barrier layer further comprises poly (alkylene terephthalate) (PAT), the furan-based polyester and PAT comprising the total weight of the polymer blend composition comprising the furan-based polyester and PAT. In contrast, a polymer blend containing 0.1 to 99.9% by weight of PAT is formed.

  In a seventh embodiment of the multilayer structure, the barrier layer comprises poly (trimethylene furandicarboxylate) (PTF) and poly (ethylene terephthalate) (PET).

  In an eighth embodiment, the multi-layer structure takes the form of a housing with a port for introducing hydrocarbon fuel in an enclosure defined by the housing.

  In a ninth embodiment, the multilayer structure takes the form of a hollow body selected from the group consisting of hoses, pipes, ducts, tubes, tube materials or conduits.

  In a tenth embodiment, an article for storage or transport of hydrocarbon fuel is provided, comprising a multilayer structure in the form of a housing with an inlet and outlet for introducing hydrocarbon fuel in a closed vessel defined by the housing, Its multi-layer structure provides a permeation barrier for hydrocarbon fuels.

  In an eleventh embodiment, the article further comprises means for closing the door, such that when the door is closed, the material is isolated from the external environment.

  In a twelfth embodiment of the article, the hydrocarbon fuel comprises one or more of ethanol, methanol, butanol, toluene, xylene, isooctane, gasoline, kerosene, liquefied petroleum, diesel and biodiesel.

  In the thirteenth embodiment, the article is selected from the group consisting of a fuel container, a fuel container with a lid, a fuel container with a sealing part, a fuel can, a fuel valve, a fuel inlet, a fuel supply part, a fuel tank and a fuel line. Take the form.

In a fourteenth embodiment, a method of reducing hydrocarbon fuel permeation through a fuel tank comprising providing a fuel tank having at least one polymer barrier layer, wherein the furan-based polyester:
a) 2,5-furandicarboxylic acid or a derivative thereof,
b) C ₂ ~C ₁₂ aliphatic diol or polyol, and c) optionally, a polyalkylene ether glycol (PAEG), multifunctional acids or multifunctional one or more of hydroxyl acid,
Derived from the method is provided.

In a fifteenth embodiment, a method for storing or transporting hydrocarbon fuel comprising providing a housing with an inlet / outlet for introducing hydrocarbon fuel in a closed vessel defined by the housing, the housing comprising: Including furan-based polyester, furan-based polyester:
a) 2,5-furandicarboxylic acid or a derivative thereof,
b) C ₂ ~C ₁₂ aliphatic diol or polyol, and c) optionally, a polyalkylene ether glycol (PAEG), multifunctional acids or multifunctional one or more of hydroxyl acid,
Derived from the method is provided.

  The present invention is illustrated by way of example and is not limited to the accompanying drawings.

FIG. 6 schematically illustrates a cross-sectional view of a portion of an exemplary multilayer structure including three layers, in accordance with the present invention. FIG. 3 schematically illustrates a cross-sectional view of a portion of an exemplary multilayer structure including at least four layers in accordance with the present invention. FIG. 6 schematically illustrates a cross-sectional view of a portion of an exemplary multilayer structure including at least five layers in accordance with the present invention.

Reference numerals shown in FIGS. 1 to 3 will be described below.
100, 200, 300: multilayer structures 110, 210, 310: barrier layers 111, 211, 311: first structure layers 221, 321: second structure layers 112, 212, 312: first bonding layer 322: second bonding layer

  The disclosures of all patents and non-patent literature are incorporated herein by reference in their entirety.

  The term “barrier” is used interchangeably with “permeability” to describe the barrier properties of hydrocarbon fuels, meaning that hydrocarbon fuels have high barrier properties when the permeability of hydrocarbon fuels is low. To do.

  The terms “barrier” and “barrier layer” as applied to a multilayer structure refer to the ability of the structure or layer to serve as a barrier to fluids (eg, gases or liquids), particularly hydrocarbon fuels.

  The term “hydrocarbon fuel permeable barrier layer” is used interchangeably with “barrier layer” and “polymer barrier layer”.

The term “fuel container” is not limited to:
● ○ Automobile, motorcycle, ship, airplane, electric generator, lawn mower tractor, snowmobile,
O Small portable devices such as line trimmers, blowers (fallen leaves & snow), pressure washers, mowers, generators, and o fuel containers attached to other household, industrial and agricultural machinery;
● portable containers such as jelly cans to supply fuel to the fuel containers; and ● containers that store the fuel used to drive such machines;
Means.

  As used herein, the term “bonding layer” refers to a polymer layer that improves adhesion between two layers, such as between a barrier layer and a structural layer.

The term “furandicarboxylic acid” is used interchangeably with furandicarboxylic acid; 2,5-furandicarboxylic acid; 2,4-furandicarboxylic acid; 3,4-furandicarboxylic acid; and 2,3-furandicarboxylic acid. The As used herein, 2,5-furandicarboxylic acid (FDCA), also known as dehydromucic acid, is a furan oxide derivative shown below.

  The term “furan 2,5-dicarboxylic acid (FDCA) or a functional equivalent thereof” refers to a suitable isomer of furandicarboxylic acid or a derivative thereof, such as 2,5-furandicarboxylic acid; 3,4-furandicarboxylic acid; means 2,3-furandicarboxylic acid or a derivative thereof; The terms “PTF” and “poly (trimethylene furandicarboxylate)” are used interchangeably and include poly (trimethylene-2,5 furandicarboxylate), poly (trimethylene-2,4 furandicarboxylate), poly (trimethylene- 2,3 furandicarboxylate), and poly (trimethylene-3,4 furan carboxylate).

  The term “biologically derived” is used interchangeably with “biologically derived” and is derived from renewable resources such as plants and contains only renewable carbon or substantially renewable carbon. Means hydrocarbon fuel compounds, such as monomers and polymers, which contain no or very little fossil fuel-based or petroleum-based carbon.

A multilayer structure is disclosed that includes a hydrocarbon fuel permeable barrier layer, a structural layer, and a tie layer disposed between the first structural layer and the barrier layer, the barrier layer comprising a furan-based polyester, Provides a permeation barrier for hydrocarbon fuels. In one embodiment, a furan-based polyester, 2,5 furandicarboxylic acid, or a derivative thereof, C ₂ -C ₁₂ aliphatic diol or polyol, optionally a polyalkylene ether glycol (PAEG), multifunctional acids or multifunctional Derived from the polycondensation of at least one of the hydrophilic hydroxyl acids.

  FIG. 1 schematically illustrates a cross-sectional view of a portion of an exemplary multilayer structure 100 that includes at least three layers in accordance with the present invention. A multilayer structure 100 shown in FIG. 1 includes a hydrocarbon fuel permeation barrier layer 110 comprising a furan-based polyester of the present disclosure and a first structural layer 111. The multilayer structure 100 also includes a first bonding layer 112 interposed between the barrier layer 110 and the first structural layer 111.

  FIG. 2 schematically illustrates a cross-sectional view of a portion of an exemplary multilayer structure 200 that includes at least four layers in accordance with the present invention. A multilayer structure 200 shown in FIG. 2 is interposed between a hydrocarbon fuel permeable barrier layer 210 containing a furan-based polyester of the present disclosure, a first structural layer 211, and between the barrier layer 210 and the first structural layer 211. A first bonding layer 212 formed thereon. The multilayer structure 200 also includes a second structural layer 221 such that the barrier layer 210 is placed between the first bonding layer 212 and the second structural layer 221.

  FIG. 3 schematically illustrates a cross-sectional view of a portion of an exemplary multilayer structure 300 that includes at least five layers in accordance with the present disclosure. The multilayer structure 300 shown in FIG. 3 is placed between a hydrocarbon fuel permeable barrier layer 310 comprising a furan-based polyester of the present disclosure, a first structural layer 311, and between the barrier layer 310 and the first structural layer 311. A first bonding layer 312. The multilayer structure 300 also includes a second bonding layer 322 such that the barrier layer 310 is placed between the first bonding layer 312 and the second bonding layer 322.

  The multilayer structure of the present invention is not limited, but other possibilities, such as unillustrated 6, 7, 8, etc., wherein at least one layer is a barrier layer comprising the furan-based polyester of the present invention. It can contain a certain layer structure.

  In one embodiment of the multilayer structure, the furan-based polyester is poly (trimethylene furandicarboxylate).

Barrier layer barrier layer is 2,5-furandicarboxylic acid or a derivative thereof, C ₂ -C ₁₂ aliphatic diol or polyol, optionally a polyalkylene ether glycol (PAEG), of polyfunctional acids or polyfunctional hydroxyl acids A furan-based polyester obtained by polymerization of a reaction mixture comprising at least one of C ₂ -C ₁₂ aliphatic diols may be linear or branched.

In the derivatives of 2,5-furandicarboxylic acid, the hydrogens at the 3- and / or 4-positions of the furan ring are, if desired, independently of one another selected from the group consisting of O, N, Si and S Optionally containing 1 to 3 heteroatoms and further optionally substituted with at least one member selected from the group consisting of -Cl, -Br, -F, -I, -OH, -NH ₂ and -SH It is, -CH _3, -C ₂ H ₅ or C ₃ -C ₂₅ linear, may be substituted with branched or cyclic alkane group. Derivatives of 2,5-furandicarboxylic acid can also be prepared by substitution of an ester or halide at one or both of the acid sites.

Examples of suitable C ₂ -C ₁₂ aliphatic diols include, but are not limited to ethylene glycol; diethylene glycol; 1,2- propanediol; 1,3-propanediol; 1,4-butanediol; 1,5 Diols; 1,6-hexanediol; 1,4-cyclohexanedimethanol; and 2,2-dimethyl-1,3-propanediol. In one embodiment, the aliphatic diol is a biologically derived C ₃ diol, such as 1,3-propanediol (BioPDO ™).

  The furan-based polyesters of the barrier layers 110, 210, 310 shown in FIGS. 1, 2 and 3 are at least one of furandicarboxylic acid or functional equivalents thereof, diol or polyol monomers, and multifunctional aromatics. It can be a copolyester (random or block) derived from at least one of acids or hydroxyl acids. The molar ratio of furandicarboxylic acid to at least one of polyfunctional aromatic acid or hydroxyl acid can be in any range, and the molar ratio of either component is greater than 1: 100 or Alternatively, it can be in the range of 1: 100 to 100: 1 or 1: 9 to 9: 1 or 1: 3 to 3: 1 or 1: 1, and a furandicarboxylic acid and a polyfunctional aromatic acid or The diol is added in an excess of 1.2 to 3 equivalents relative to the total charged acid, including at least one of the hydroxyl acids.

  Examples of suitable multifunctional acids include, but are not limited to, terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanoic acid, 1,4-cyclohexanedicarboxylic acid, maleic acid, succinic acid, 2,6 -Naphthalenedicarboxylic acid and 1,3,5-benzenetricarboxylic acid.

  Examples of suitable hydroxy acids include, but are not limited to, glycolic acid, hydroxybutyric acid, hydroxycaproic acid, hydroxyvaleric acid, 7-hydroxyheptanoic acid, 8-hydroxycaproic acid, 9-hydroxynonanoic acid, or lactic acid; or pivalolactone , Ε-caprolactone or hydroxy acids derived from L, L, D, D or D, L lactide.

Furan-based copolyester can be produced in the polymerization monomer composition, are included in addition to the C ₂ -C ₁₂ aliphatic diols mentioned above, Examples of other diols and polyols monomers include, but are not limited to, 1, 4-benzenedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, cyclohexyldimethanol, poly (ethylene glycol), poly (tetrahydrofuran), 2,5-di (hydroxymethyl) tetrahydrofuran, Examples include isosorbide, isomannide, glycerol, pentaerythritol, sorbitol, mannitol, erythritol, and threitol. Present in furan-based copolyester, a molar ratio of C ₂ -C ₁₂ aliphatic diol and other diols and polyols monomers can be any range, for example, the molar ratio of either component is 1 : 100, or alternatively may range from 1: 100 to 100: 1 or 1: 9 to 9: 1 or 1: 3 to 3: 1 or 1: 1.

  Exemplary furan-based polyesters that are copolymers derived from furandicarboxylic acids, at least one of diol or polyol monomers, and at least one of multifunctional acids or hydroxyl acids include, but are not limited to, Copolymer of 3-propanediol, 2,5-furandicarboxylic acid and terephthalic acid; copolymer of 1,3-propanediol, ethylene glycol and 2,5-furandicarboxylic acid; 1,3-propanediol, 1,4-butane Copolymer of diol and 2,5-furandicarboxylic acid; copolymer of 1,3-propanediol, 2,5-furandicarboxylic acid and succinic acid; copolymer of 1,3-propanediol and 2,5-furandicarboxylic acid; 1 , 3-propanediol, 2,5-fur Copolymer of dicarboxylic acid and adipic acid; copolymer of 1,3-propanediol, 2,5-furandicarboxylic acid and sebacic acid, copolymer of 1,3-propanediol, 2,5-furandicarboxylic acid and isosorbide; Mention may be made of copolymers of 3-propanediol, 2,5-furandicarboxylic acid and isomannide.

  Suitable furan-based polyesters for the barrier layer include, but are not limited to, poly (trimethylene-2,5-furandicarboxylate) (PTF), poly (butylene-2,5-furandicarboxylate) (PBF), or poly (Ethylene-2,5-furandicarboxylate) (PEF).

式中、ｎ＝１０〜１０００または５０〜５００または２５〜１８５または８０〜１８５である。 Barrier layers 110, 210, 310 shown in FIGS. 1, 2 and 3 are suitable isomers of 1,3-propanediol and furandicarboxylic acid or derivatives thereof, such as 2,5-furandicarboxylic acid, 2,4-flange. Poly (trimethylene furandicarboxylate) (PTF) derived from polycondensation of carboxylic acids, 3,4-furandicarboxylic acids, 2,3-furandicarboxylic acids or derivatives thereof may be included. The PTFs shown below are derived from the polymerization of 2,5-furandicarboxylic acid or its acid form derivatives and 1,3-propanediol.

In the formula, n = 10 to 1000, 50 to 500, 25 to 185, or 80 to 185.

  The poly (trimethylene furandicarboxylate) (PTF) disclosed herein may have a number average molecular weight in the range 1960-196000 or 1960-98000 or 4900-36260. Also, the PTF can have a degree of polymerization of 10 to 1000 or 50 to 500 or 25 to 185 or 80 to 185.

  The barrier layers 110, 210, 310 shown in FIGS. 1, 2 and 3 comprise 2,5-furandicarboxylic acid or functional equivalents thereof, at least one of diol or polyol monomers, at least one polyalkylene ether glycol (PAEG). A furan-based polyester, which is a copolyester derived from), the molar ratio of diol or polyol to polyalkylene ether glycol being at least 2: 0.0008. The molar amounts of furandicarboxylic acid, 1,3 propanediol and at least one polyalkylene ether glycol (PAEG) are in any suitable range, for example from 1: 2: 0.0008 to 1: 2: 0.145, respectively. Can be in range.

  The barrier layers 110, 210, 310 shown in FIGS. 1, 2 and 3 can further comprise PTFs such that the furan-based polyester is different from the PTF, which furan-based polyester and PTF are the furan-based polyester and PTF. To form a polymer blend comprising 0.1 to 99.9%, or 5 to 75%, or 10 to 50% by weight of PTF relative to the total weight of the polymer blend composition.

The barrier layers 110, 210, 310 shown in FIGS. 1, 2 and 3 can further comprise poly (alkylene terephthalate) (PAT), the furan-based polyester and PAT being a polymer comprising furan-based polyester and PAT. A polymer blend is formed comprising 0.1 to 99.9% or 5 to 75% or 10 to 50% by weight of PAT relative to the total weight of the blend composition. Poly (alkylene terephthalate) comprises units derived from terephthalic acid and C ₂ -C ₁₂ aliphatic diols.

  The multilayer barrier layer has a thickness in the range of 0.5-50% or 1-25% or 1-10% or 1-5% of the total thickness of the multilayer structure to provide a permeation barrier for hydrocarbon fuels. And the total thickness of the multi-layer structure can range from 10 to 100000 microns or 100 to 10,000 microns or 500 to 8500 microns or 10 to 2000 microns. The thickness of the barrier layer in the multilayer structure depends on several factors, such as the intended use of the article comprising the multilayer structure. For example, the thickness of the barrier layer can be 10% of the total bottle and / or tank thickness to provide optimal hydrocarbon barrier and mechanical properties, such as 20-50% of hoses and pipes, etc. More than that. The multilayered barrier layer may have a thickness in the range of 50 to 5000 microns, or 100 to 2500 microns, or 100 to 1000 microns or 100 to 500 microns.

Structural layer The structural layers, for example, the first structural layers 111, 211, 311, 221, and 321 and the second structural layers 221 and 321 shown in FIGS. 1 to 3 are formed by extrusion molding, bonding, or any other means. It may contain a suitable polymer that can maintain its shape after. Suitable polymers for use in the structural layer include, but are not limited to, polyolefins, polyesters, and polyamides.

  At least one of the first structural layers 111, 211, 311 or the second structural layers 221, 321 may include a polyolefin. Polyolefin homopolymers and copolymers are based on α-olefins such as, but not limited to, ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene or 4-methyl-1-pentene. To do. Suitable polyolefins include, but are not limited to, polypropylene, biaxially oriented polypropylene (BOPP), polyethylene (PE), high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium Density polyethylene (MDPE), ultra high molecular weight polyethylene (UHMWPE), crosslinked polyethylene (PEX), very low density polyethylene (VLDPE), polyisobutylene (PIB), polymethylpentene (PMP), polybutene, polyolefin elastomer (POE), ethylene -Propylene rubber (EPR), and blends of combinations of two or more thereof.

  At least one of the first structural layers 111, 211, 311 or the second structural layers 221, 321 may include polyester. Suitable polyesters include, but are not limited to, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene-2,5-furandicarboxylate (PEF), polybutylene-2,5- PET copolymer using furan carboxylate (PBF), polyethylene-2,6-naphthalate (PEN), isophthalic acid, cyclohexyldimethanol, or 2,2,4,4-tetramethyl-1,3-cyclobutanediol as a comonomer , And combinations of two or more thereof.

  At least one of the first layers 111, 211, 311 or the second structural layers 221, 321 includes a polyamide such as, but not limited to, an aliphatic polyamide, an aromatic polyamide (polyaramid), a polyamide-imide or a mixture thereof. obtain. Suitable polyamides include, but are not limited to, polycapramide (nylon 6), polyundecanamide (nylon 11), polydodecanamide (nylon 12), polyethylene adipamide (nylon 26), polytetramethylene adipamide (nylon 46 ), Polyhexamethylene adipamide (nylon 66), polyhexamethylene azepamide (nylon 69), polyhexamethylene sebacamide (nylon 610), polyhexamethylene undecamide (nylon 611), polyhexamethylene dodeca Amide (nylon 612), polyhexamethylene hexadecanamide (nylon 616), polyhexamethylene octadecanide (nylon 618), nylon 6/66 copolymer, nylon 6/12/66 terpolymer, polyhexamethylene terephthalate Mido (nylon 6T), polyhexamethylene isophthalamide (nylon 6I), polynonamethylene dodecamide (nylon 912), polydecamethylene decamide (nylon 1010), polydecamethylene dodecamide (nylon 1012), polydodecamethylene dodeca Amide (nylon 1212), poly (p-phenylene terephthalamide), poly (meta-phenylene terephthalamide), polymetaxylene adipamide (nylon MXD6), polytrimethylhexamethylene terephthalamide (nylon TMHT), polybis (4- Aminocyclohexyl) methane dodecamide (nylon PACM12), polybis (3-methyl-4-aminocyclohexyl) methanedecanamide (nylon dimethyl PACM12), polydecamethylene terephthalami (Nylon 10T), polyundecamethylene terephthalamide (nylon 11T), polydodecamethylene terephthalamide (nylon 12T), its copolymers and terpolymers (such as nylon 6/66/12) and the like.

  The first structural layers 111, 211, 311 and the second structural layers 221, 321 may have the same composition or different compositions.

  The thicknesses of the first structural layers 111, 211, 311 and the second structural layers 221, 321 may be the same or different. The thickness of the structural layer can range from 100 to 100,000 microns, or from 100 to 10,000 microns, or from 100 to 6000 microns.

Bonding Layer The bonding layers 112, 212, 312, 322 shown in FIGS. 1, 2 and 3 comprise one or more olefin copolymers. The bonding layers 112, 212, 312, 322 are placed between the barrier layer and at least one further layer of either the first structural layer or the second structural layer. The first tie layer 312 and the second tie layer 322 may have the same composition or different compositions. The one or more olefin copolymers include, but are not limited to, propylene copolymers, ethylene copolymers, and mixtures thereof.

  “Propylene copolymer” means a polymer comprising repeating units derived from propylene and at least one further monomer. Suitable propylene-based copolymers include, but are not limited to, other alpha as monomers such as ethylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene or 4-methyl-1-pentene. -Copolymers of olefins and propylene. The copolymer can be either a random copolymer or a block copolymer.

  “Ethylene copolymer” means a polymer comprising repeating units derived from ethylene and at least one further monomer.

  The one or more ethylene copolymers contained in the multi-layer tie layer are ethylene alpha olefin, ethylene vinyl acetate copolymer, ethylene maleic anhydride copolymer, ethylene acrylic acid (or a neutralized salt form of the acid) copolymer, It may be selected from ethylene methacrylic acid (or a neutralized salt form of the acid) copolymer, ethylene glycidyl (meth) acrylate copolymer, ethylene alkyl (meth) acrylate copolymer, or a combination of two or more thereof. “Alkyl (meth) acrylate” means alkyl acrylate and / or alkyl methacrylate. An ethylene alkyl (meth) acrylate copolymer is a thermoplastic ethylene copolymer derived from the copolymerization of an ethylene comonomer and at least one alkyl (meth) acrylate comonomer, the alkyl group of which has 1 to 10 carbon atoms, preferably 1 Contains ~ 4. More preferably, the ethylene copolymer contained in the tie layer is ethylene α-olefin, ethylene vinyl acetate copolymer, ethylene methyl (meth) acrylate copolymer, ethylene ethyl (meth) acrylate copolymer, ethylene butyl (meth) acrylate copolymer, or 2 thereof. It is selected from a combination of more than types.

  If the ethylene copolymer used for the tie layer is an ethylene alpha olefin copolymer, it comprises ethylene and an alpha olefin of 3 to 20 carbon atoms. Preferred alpha olefins contain 4 to 8 carbon atoms.

  Generally, the density of the ethylene alpha olefin copolymer is in the range of 0.860 to 0.925 g / cc, preferably 0.860 to 0.910 g / cc, more preferably 0.880 to 0.905 g / cc. Resins made by Ziegler-Natta type catalysts and by metallocene or single site catalysts are included provided that the catalyst is within the described density range. Metallocene or single site catalyst resins useful herein include (i) an I-10 / I-2 ratio of less than 5.63 and an Mw / Mn of greater than (I-10 / I-2) -4.63 A resin having (polydispersity), and (ii) a resin having an I-10 / I-2 ratio of 5.63 or more and a polydispersity of (I-10 / I-2) -4.63 or less. . Preferably, the group (ii) metallocene resin has a polydispersity greater than 1.5 but not greater than (I-10 / I-2) -4.63. Suitable conditions and catalysts that can produce substantially linear metallocene resins are described in US Pat. No. 5,278,272. This reference provides a complete description of the measurement of the known hydrodynamic parameters I-10 and I-2, which are the flow values under different load and shear conditions. Details of measurements of known Mw / Mn ratios as determined by gel permeation chromatography (GPC) are also provided.

  When the tyrene copolymer used in the tie layer is an ethylene vinyl acetate copolymer, the relative amount of copolymerized vinyl acetate units is 2-40% by weight, preferably 10-40% by weight, the weight percentage of which is For total weight. A mixture of two or more different ethylene vinyl acetate copolymers can be used as a component of the tie layer instead of a single copolymer.

  When the ethylene copolymer is an alkyl (meth) acrylate, the relative amount of copolymerized alkyl (meth) acrylate units is 0.1 to 45% by weight, preferably 5 to 35% by weight, and more preferably 8 to 28%. The weight percentage is based on the total weight of the ethylene copolymer.

  The one or more olefin homopolymers and / or copolymers can be modified copolymers, meaning that the copolymer is grafted with and / or copolymerized with organic functional groups. The modified polymer used in the tie layer can be modified with acid, anhydride and / or epoxide functional groups. Examples of acids and anhydrides used to modify polymers, which can be mono-, di-, or polycarboxylic acids are acrylic acid, methacrylic acid, maleic acid, maleic acid monoethyl ester, fumaric acid, furric acid, itaconic acid , Crotonic acid, 2,6-naphthalenedicarboxylic acid, itaconic anhydride, maleic anhydride and substituted maleic anhydrides such as dimethylmaleic anhydride or citrotonic anhydride, nadic acid anhydride, nadic methyl anhydride, and tetrahydro A phthalic anhydride or a combination of two or more thereof, maleic anhydride is preferred.

  When an acid modified polymer is used, it contains 0.05 to 19% by weight of acid, the weight percent being based on the total weight of the modified polymer.

  When an anhydride modified polymer is used, it contains 0.03 to 2% by weight, preferably 0.05 to 2% by weight of anhydride, the weight percent being based on the total weight of the modified ethylene polymer.

  Examples of epoxides used for polymer modification are unsaturated epoxides containing 4 to 11 carbon atoms, such as glycidyl (meth) acrylate, allyl glycidyl ether, vinyl glycidyl ether and glycidyl itaconate, glycidyl (meth) acrylate Is particularly preferred. The epoxide modified ethylene copolymer preferably contains 0.05 to 15% by weight of epoxide, the weight percent being based on the total weight of the modified ethylene copolymer. Preferably, the epoxide used to modify the ethylene copolymer is glycidyl (meth) acrylate. The ethylene / glycidyl (meth) acrylate copolymer may further contain copolymerized units of an alkyl (meth) acrylate having 1 to 6 carbon atoms and an α-olefin having 1 to 8 carbon atoms. Typical alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, or 2 More than one type of combination can be mentioned. Of note are ethyl acrylate and butyl acrylate. The alpha olefin can be selected from the group of propylene, octene, butene and hexane, in particular propylene.

  Preferably, the modified ethylene copolymer contained in the tie layer is modified with acid, anhydride and / or glycidyl (meth) acrylate functional groups.

  Exemplary ethylene-based copolymers include, but are not limited to, polyethylene-co vinyl acetate, polyethylene-co-methyl acrylate, polyethylene-co-maleic anhydride, polyethylene-co-acrylate (ie, methyl acrylate, ethyl acrylate, butyl Acrylate, etc.), polyethylene-co-glycidyl acrylate, polyethylene-co-glycidyl methacrylate, polyethylene-co-vinyl alcohol, polyethylene-co-acrylic acid; polyethylene-co-acrylic acid sodium salt, polyethylene-co-methyl methacrylate, polyethylene- Examples include co-methacrylic acid and polyethylene-co-methacrylic acid sodium salt.

  Copolymers and modified polymers useful in the present invention include E.I. I. It is commercially available from du Pont de Nemours and Company, (Wilmington, DE) under the trademarks Elvax®, Elvaloy®, Bynel®.

  A tie layer can also be used to improve adhesion between layers comprising polar materials such as polyester and polyamide. Examples of such tie layers include, but are not limited to, polyacrylates, aromatic polyesters, aliphatic polyesters, aliphatic-aromatic copolyesters, polyamides, polyester amides, polyvinyl alcohol, aliphatic polycarbonates, aromatic polycarbonates, polymaleic anhydride Or grafted polymaleic anhydride, polyvinyl acetate, polyvinyl acetate-co-maleic anhydride, polyvinyl alcohol-co-vinyl acetate, polyacrylate-co-vinyl acetate, polyacrylate-co vinyl alcohol, polyacrylate-co -Maleic anhydride, polyvinyl alcohol-co-maleic anhydride, polyacrylic acid or neutralized salt form thereof, polyacrylic acid-co-vinyl alcohol, polyacrylic acid-co-vinyl acetate , Polyacrylic acid -co- maleic anhydride or a blend of two or more components, and the like.

  The thickness of the first bonding layers 112, 212, 312 and the second bonding layers 222, 322 may be the same or different. The thickness of the tie layer can range from 1-1000 microns or 1-500 microns or 1-100 microns or 1-25 microns or 1-10 microns or 1-5 microns or less than 1 micron.

Additives One or more of the multilayer structures 100, 200, 300, namely the barrier layers 110, 210, 310 described above; one or more of the structural layers 111, 211, 221, 311, 321; and 1 One or more of the species or types of tie layers 112, 212, 312, 322 include, but are not limited to, antioxidants, plasticizers, thermal stabilizers, UV absorbers, antistatic agents, lubricants, colorings. One or more additives such as agents, fillers and heat stabilizers may be included. The amount of additive present in each of the barrier layer, the structural layer and the tie layer can range from 1 ppm to 5% or 1 ppm to 3% or 1 ppm to 1%.

  Suitable antioxidants include, but are not limited to, 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, 4,4′-thiobis- (6-t-butylphenol). ), 2,2′-methylene-bis- (4-methyl-6-tert-butylphenol), octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate, 4, 4'-thiobis- (6-t-butylphenol) and the like.

  Suitable UV absorbers include, but are not limited to, ethylene-2-cyano-3,3′-diphenyl acrylate, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy -5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2-hydroxy-4-methoxybenzophenone, 2,2 Examples include '-dihydroxy-4-methoxybenzophenone and 2-hydroxy-4-methoxybenzophenone.

  Suitable plasticizers include, but are not limited to, phthalate esters such as dimethyl phthalate, diethyl phthalate, dioctyl phthalate, waxes, liquid paraffin, phosphate esters.

  Suitable antistatic agents include, but are not limited to, pentaerythritol monostearate, sorbitan monopalmitate, sulfated polyolefin, polyethylene oxide, carbon wax, and the like.

  Suitable lubricants include but are not limited to ethylene bisstearamide, butyl stearate and the like.

  Suitable colorants include, but are not limited to, carbon black, phthalocyanine, quinacridone, indoline, azo pigments, bengara and the like.

  Suitable fillers include but are not limited to glass fiber, asbestos, ballastonite, calcium silicate, talc, montmorillonite and the like.

Articles In one aspect, the multilayer structure disclosed hereinabove takes the form of a housing with an inlet / outlet for introducing hydrocarbon fuel in a closed vessel defined by the housing, the multilayer structure being a hydrocarbon fuel. Provides a permeation barrier for

  The housing may take the form of a hose, pipe, duct, tube, tubing or conduit.

  The housing may take the form of a fuel container, a fuel container with a lid, a fuel container with a seal, a fuel can, a fuel valve, a fuel inlet, a fuel supply, a fuel tank and a fuel line.

  Suitable hydrocarbon fuels include, but are not limited to, ethanol, methanol, butanol, toluene, xylene, isooctane, gasoline, kerosene, liquefied petroleum, diesel, biodiesel and mixtures thereof.

  In another aspect, an article for storage or transportation of hydrocarbon fuel comprising a multilayer structure as disclosed above in the form of a housing with an inlet and outlet for introducing hydrocarbon fuel in a closed vessel defined by the housing. And its multilayer structure provides a permeation barrier for hydrocarbon fuels. The article may further comprise means for closing the door, such that when the door is closed, the material is isolated from the external environment. The article may take a form selected from the group consisting of a fuel container, a fuel container with a lid, a fuel container with a seal, a fuel can, a fuel valve, a fuel inlet, a fuel refill, a fuel tank and a fuel line.

In one embodiment, the article comprises a multilayer structure in the form of a gas tank and having HDPE as a structural layer, a furan-based polyester of the present disclosure as a barrier layer, and an ethylene copolymer as a tie layer. The following layered structure:
● HDPE / ethylene copolymer / furan-based polyester ● HDPE / ethylene copolymer / PTF
● HDPE / ethylene copolymer / furan-based polyester / ethylene copolymer / HDPE
● HDPE / ethylene copolymer / PTF / ethylene copolymer / HDPE
1 type or multiple types of these are formed.

  Articles in the form of gas tanks, including furan-based polyester as a barrier layer, include automobiles, motorcycles, ships, airplanes, lawn mowers, snowmobiles; small portable devices such as line trimmers, blowers (fallen leaves & snow), pressure wash Can be attached to equipment, mowers, generators; other household, industrial and agricultural machines. This article can take the form of a portable container such as a jelly can. This article can take the form of a container for storing fuel.

In other embodiments, the article is in the form of a fuel line and includes a multilayer structure with or without a tie layer, with nylon as a structural layer and PTF as a barrier layer, and having the following structure:
● Nylon / bond / furan-based polyester ● Nylon / bond / PTF
● Nylon / bond / furan-based polyester / bond / nylon ● One or more of nylon / bond / PTF / bond / nylon are formed.

  In the form of a fuel line, containing furan-based polyester as a barrier layer, this article is a car, motorcycle, ship, airplane, lawn mower tractor, snowmobile; small portable devices such as line trimmers, blowers (fallen leaves & snow) , Pressure washer, mower, generator; other household, industrial and agricultural machines.

  The total thickness of an article for storage or transportation of hydrocarbon fuel, such as a fuel container, is preferably 10-100,000 microns or 100-10000 microns or 500-8500 microns or 1000-7000 microns. Note that the thickness is the average thickness of the fuel container measured at the body. If the total thickness is excessively large, the weight becomes too high, which has a disadvantageous effect on the fuel consumption of the automobile and also increases the cost of the fuel container. On the other hand, when the total thickness is excessively thin, sufficient rigidity is not maintained, and there is a problem that the fuel container is easily broken. Therefore, it is important to determine the thickness according to the capacity of the fuel container and the purpose of use.

  The method for producing the article disclosed above in the present specification, particularly the fuel container made of the multilayer structure of the present invention is not particularly limited, and examples thereof include extrusion molding, blow molding, and injection molding. And molding methods performed in the field of general polyolefin or polyester or polyamide. In particular, common extrusion molding and common injection molding are preferred. Of these, shared extrusion blow molding is most preferred.

  A method for storing or transporting hydrocarbon fuel comprising providing a housing with an inlet and outlet for introducing hydrocarbon fuel in a closed vessel defined by the housing, the housing comprising the carbonization disclosed above. A method is disclosed that includes a furan-based polyester as a hydrogen fuel barrier layer.

  A method of transporting hydrocarbon fuel with minimal permeation through a multilayer tube or hose, wherein the hydrocarbon fuel is introduced into the multilayer tube or hose through the inlet and discharged through the outlet, the multilayer tube being disclosed above. Disclosed is a method comprising furan-based polyester as the hydrocarbon fuel barrier layer. The hydrocarbon fuel is a hydrocarbon fluid and the multilayer tube is a fuel line.

  Disclosed is a method for reducing fuel permeation through a fuel tank comprising providing a fuel tank having a furan-based polyester as the hydrocarbon fuel barrier layer disclosed above.

  In one embodiment, the fuel line and fuel tank include poly (trimethylene furandicarboxylate) as a hydrocarbon fuel barrier layer.

  As used herein, “comprises”, “comprising”, “includes”, “including”, “has”, “having” The term “or any other variation” is intended to include non-exclusive inclusions. For example, a process, method, article, or device that includes a list element is not necessarily limited to only those elements, but other elements that are not explicitly specified, or others specific to such a process, method, article, or device. May contain elements of Further, unless expressly specified to the contrary, “or” means inclusive or rather than exclusive or. For example, condition A or B is as follows: A is true (or present) and B is false (or does not exist), A is false (or does not exist) and B is true (or Present), and both A and B are true (or present);

  As used herein, the phrase “one or more” is intended to include non-exclusive inclusions. For example, one or more of A, B, and C can be: A only, B only, C only, A and B combination, B and C combination, A and C combination, or A, Any one of a combination of B and C;

  “One (a)” or “one” (an) is also used to describe the elements described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This specification should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

  Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the disclosed composition embodiments, suitable methods and materials are described below. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

  In the above detailed description, the concepts are disclosed with reference to specific embodiments. However, one of ordinary skill in the art appreciates that various modifications and changes can be made without departing from the scope of the present disclosure as set forth in the claims below.

  Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. However, the benefit, advantage, solution to the problem, and one or more features that may or may make any benefit, advantage, or solution, any or all embodiments It is not to be construed as an important, required, or essential feature of.

  It should be understood that certain features are described herein in the context of separate embodiments for ease of understanding and may also be provided in combination in one embodiment. Conversely, various features that are briefly described in the context of one embodiment can also be provided separately or in subcombinations. Further, reference to values stated in ranges include each and every value within that range.

  The concepts disclosed herein are further described in the following examples, which do not limit the scope of the teachings of the invention as set forth in the claims.

  The examples described herein relate to a hydrocarbon fuel permeation barrier layer comprising a furan-based polyester. The following discussion explains how a multilayer structure comprising a furan-based polyester and a run-based polyester is formed for use as a hydrocarbon fuel barrier layer.

Test Method Molecular Weight by Size Exclusion Chromatography Size Exclusion Chromatography System, Alliance 2695 ™ (Waters Corporation, Milford, Mass.) Is a Waters 414 ™ differential refractive index detector, multi-angle light scattering photometer DAWN Heleos II (Wyatt Technologies, Santa Barbara, Calif.), And ViscoStar ™ differential capillary viscometer detector (Wyatt). The data collection and data processing software was Wyatt's Astra-version 5.4. There are two columns used; one is a Shodex GPC HFIP-806M ™ styrene-divinylbenzene column with an exclusion limit of 2 × 10 ⁷ and a theoretical plate number of 8,000 / 30 cm; It was a Shodex GPC HFIP-804M ™ styrene-divinylbenzene column with × 10 ⁵ and a theoretical plate number of 10,000 / 30 cm.

  Test pieces in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) containing 0.01 M sodium trifluoroacetate by mixing for 4 hours at 50 ° C. with gentle stirring Was subsequently dissolved and subsequently filtered through a 0.45 μm PTFE filter. The concentration of the solution was about 2 mg / mL.

  Data were taken on a chromatograph set at 35 ° C. at a flow rate of 0.5 ml / min. The injection volume was 100 μl. The implementation time was 80 minutes. Data processing was performed incorporating data from all three detectors described above. Eight scattering angles were used with a light scattering detector. A standard for column calibration was not included in the data processing.

Molecular weight by intrinsic viscosity Goodyear R-103B Equivalent IV method using T-3, Selar (R) X250, Sorona (R) 64 as calibration standard with Viscotek (R) Forced Flow viscometer Model Y-501C Was used to determine the intrinsic viscosity (IV). Methylene chloride / trifluoroacetic acid was the solvent carrier.

Thermal Analysis Glass transition temperature (T _g ) and melting point (T _m ) were determined by differential scanning calorimetry (DSC) performed according to ASTM D3418-08.

¹ H-NMR spectroscopy ¹ H-NMR spectra were recorded by 400 MHz NMR in either deuterated hexafluoroisopropanol (HFIP-d) or tetrachloroethane (tce-d2). Proton chemical shifts are reported in the low magnetic field ppm of TMS using deuterated solvent resonance as an internal standard.

Gas interception test Standard test The permeation to the hydrocarbon fuel mixture was tested at a test temperature of 40 ° C. according to SAE International ™ surface vehicle standard J2659. The sample produced was a mixture of methanol (15%), toluene (42.5%) and isooctane (42.5%), against CM15, or ethanol (10%), toluene (45%) and isooctane Tested against CE10, which is a (45%) mixture. CM15 is considered a more aggressive fuel mixture due to the small molecular size of methanol (MeOH) versus ethanol (EtOH). Results are expressed in g-mm / m ₂ -day. The total thickness of the multilayer (3 and 4 layers) structure was used to calculate the transmittance of the multilayer structure.

Adhesion Test A test sample cut in accordance with ASTM D882, and the adhesion between different layers of the multilayer structure was evaluated in accordance with ASTM F904.

Materials The 1,3-propanediol (bioPDO ™) and 10 mil thick Kapton ™ polyimide films used in the following examples were obtained from DuPont Company (Wilmington, DE) and were otherwise Unless otherwise specified, it was used as received. PET AA72 poly (ethylene terephthalate) 0.82IV (containing 1.9 mol% isophthalic acid) was obtained from NanYa and used as received. Titanium (IV) isopropoxide, ethylene glycol, and 1,4-butanediol were obtained from Aldrich and used as received. 2,5-furandimethyl ester (FDME) was obtained from Sarchem labs (Farmingdale, NJ) and used as received.

  EVOH, Eval (R) F171B (32 mol% ethylene) and Eval (R) J102 (32 mol% ethylene) were obtained from Kuraray America (Houston, TX) and used as received.

  Two commercially available high density polyethylene (HDPE) were used as received as the structural layer. Paxon 46-055 (melt flow index (190 ° C./2.16 kg) <0.10 g / 10 min) was obtained from ExxonMobil, used for multilayer laminates, and is called HDPE-PE. A lower viscosity, HDPE, Sclair 2907 (melt flow index (190 ° C./2.16 kg) approximately 4.9 g / min) was obtained from Nova Chemicals and used for coextrusion and is referred to as HDPE-SN. Extrusion grade homopolymer polypropylene (PP), PAG3Z-050 (melt flow index (190 ° C./2.16 kg) about 3.5 g / 10 min) was obtained from Flint Hills.

  Commercial bonding layers: Bynel® 21E533 (anhydrous modified ethylene acrylate), Bynel® E418 (anhydrous modified ethylene vinyl acetate), Bynel® 22E999 (modified ethylene acrylate), Bynel 50E662 (anhydrous) Product modified homopolypropylene), Elvaloy® AS (ethylene / n butyl acrylate / glycidyl methacrylate terpolymer), Fusbond® N525 and Bynel® 41E754 (anhydrous modified ethylene copolymer). DuPont Company (Wilmington) , DE) and used as received.

Comparative Example A-Production of Compression Molded PET Film PET AA72 was compression molded into a film with a thickness of 0.1 to 0.12 millimeters using a hydraulic platen press. The polymer pellets were placed in a 15 × 15 cm frame supported on Kapton® film. The polymer sample and Kapton® film were placed between two sheets of glass fiber reinforced Teflon® and then between two brass sheets and placed on a preheated Pasadena press. The press was preheated to the desired temperature (210 ° C for PBF, 230 ° C for PTF, 250 ° C for PEF, and 260 ° C for CE-PET) and the film sandwich was placed between the platens. . The platen was subjected to a pressure of 20,000 psig for 5-8 minutes. The film sandwich was removed and placed between two cooling plates for rapid cooling. The manufactured and quenched film was removed from the Teflon® sheet and its transmission was measured. DSC confirmed that the film so produced was completely amorphous and no melting was confirmed, ie, melting enthalpy << 1 J / g.

  The compression molded PET film was analyzed for permeation to the CM15 hydrocarbon fuel mixture and the results are summarized in Table 1.

オーバーヘッドスターラーおよび蒸留凝縮器を備えた、予め乾燥させた５００ｍＬ三つ口ケトル反応器に、２，５−フランジメチルエステル（１４７．３ｇ，０．８モル）、およびｂｉｏＰＤＯ（商標）（１０９．５ｇ，１．４４モル）を装入した。窒素パージをフラスコに適用し、温度２３℃に維持した。５０ｒｐｍにて撹拌を開始してスラリーが形成された。撹拌しながら、フラスコを合計３サイクルの間、０．１３ＭＰａまで排気し、次いでＮ₂ガスで再加圧した。最初の排気および再加圧後、チタン（ＩＶ）イソプロポキシド（９３ｍｇ）を添加した。 Example 1: Compression molded poly (trimethylene-2,5-furandicarboxylate) (PTF) film used as a hydrocarbon fuel barrier layer Stage 1A: High molecular weight poly (trimethylene-2,5-furandicarboxylate) (PTF) ) Synthesis

A pre-dried 500 mL three-neck kettle reactor equipped with an overhead stirrer and distillation condenser was charged with 2,5-furandimethyl ester (147.3 g, 0.8 mol) and bioPDO ™ (109.5 g). , 1.44 mol). A nitrogen purge was applied to the flask and maintained at a temperature of 23 ° C. Agitation was started at 50 rpm to form a slurry. While stirring, the flask was evacuated to 0.13 MPa for a total of 3 cycles and then repressurized with N ₂ gas. After initial evacuation and repressurization, titanium (IV) isopropoxide (93 mg) was added.

  After 3 cycles of evacuation and repressurization, the flask was submerged in a preheated liquid metal bath set at 160 ° C. The flask contents were agitated for 20 minutes after placing it in a liquid metal bath, causing melting of the solid components. Next, the stirring speed was increased to 180 rpm and the liquid metal bath set point was increased to 160 ° C. After about 20 minutes, the bath reached that temperature, after which the metal bath set point was raised to 180 ° C. After about 20 minutes, the bath reached that temperature. The flask was then maintained at 180 ° C. for an additional 45-60 minutes while stirring at 180 rpm to distill off most of the methanol formed in the reaction. Following the 180 ° C maintenance period, the metal bath set point was raised to 210 ° C. After about 20 minutes, the bath reached that temperature. The flask was then maintained at 210 ° C. with stirring at 180 rpm for an additional 45-60 minutes, after which the nitrogen purge was stopped and additional titanium (IV) isopropoxide (93 mg) was added and stirring continued for 10 seconds. A vacuum was gradually applied in steps of about 1330 Pa each time. After about 60 minutes, the vacuum reached 6500-8000 Pa. The stirring speed was maintained at 50-180 rpm and the metal bath set point was raised to 250 ° C. After about 20 minutes, the bath reached temperature and maintained that condition for about 3 hours.

At regular intervals, the stirring speed was increased to 180 rpm and then the stirrer was turned off. The stirrer was restarted and the applied torque was measured about 5 seconds after starting. When a torque of 75 N / cm or more was confirmed, stirring was stopped and the reaction was stopped by removing the flask from the liquid metal bath. The polymer produced was recovered by lifting the overhead stirrer from the bottom of the reaction vessel, removing the kettle, and decanting under a stream of nitrogen gas. Using a Wiley mill, the recovered polymer was cut to form pellets that were cooled with liquid nitrogen. The polymer pellets so produced were dried at 115 ° C. for 24 hours under vacuum and under a weak nitrogen stream. Yield was about 120 g. T _g was about 58 ° C. (DSC, 5 ° C./min, second heating), and T _m was about 176 ° C. (DSC, 5 ° C./min, second heating). ¹ H-NMR (TCE-d) δ: 7.05 (s, 2H), 4.40 (m, 4H), 2.15 (m, 2H). M _n (SEC) about 15200D, PDI 1.85. IV about 0.75 dL / g.

Step 1B: Production of PTF Film by Compression Molding A procedure similar to that described in Comparative Example A was used, except that the press was preheated to 230 ° C. for PTF instead of 260 ° C. for PET. A compression molded film was manufactured from the PTF polymer manufactured in Step 1A.

  The compression molded PTF film was analyzed for permeation to CM15 and CE10 hydrocarbon fuel mixtures and the results are shown in Tables 1 and 2, respectively.

Example 2: Compression molded poly (butylene-2,5-furandicarboxylate) (PBF) film used as a hydrocarbon fuel barrier layer Stage 2A: From 2,5-furandimethyl ester, and 1,4-butanediol Synthesis of Polyester, PBF Using Tyzor® TPT (210 μL) as the catalyst, using the same settings as used in Step 1A of Example 1, except that the monomers are different: , 4-butanediol (146.8 g, 1.63 mol) and FDME (150 g, 0.81 mol) were polymerized. The only difference was that the final condensation set temperature was 240 ° C. The recovered polymer yield was about 120 g. T _g was about 39 ° C. and T _m was about 169 ° C. (second heating, 10 ° C.). ¹ H-NMR (tce-d) δ: 7.30 (m, 2H), 4.70-4.30 (m, 4H), 2.0 (m, 4H). _Mn (SEC) about 16800D, PDI3.56 (SEC). IV about 1.12 dL / g.

Step 2B: Production of PBF film by compression molding Similar to the procedure described in Comparative Example A, except that instead of 260 ° C for PET, the press was preheated to a target temperature of 210 ° C for PBF. A compression molded film was produced from the PBF polymer produced in Stage A using the procedure.

  Compression molded PBF films were analyzed for permeation through CM15 and CE10 hydrocarbon fuel mixtures and the results are shown in Tables 1 and 2, respectively.

Example 3: Compression molded poly (ethylene-2,5-furandicarboxylate) (PEF) film used as a hydrocarbon fuel barrier layer Stage 3A: Polyester from 2,5-furandimethyl ester and ethylene glycol, PEF Synthesis (PEF)
Except that the monomers are different, using the same settings as used in Example 1, using Tyzor® TPT (180 μL) as the catalyst, ethylene glycol (101.2 g, 1.63) Mol) and FDME (150 g, 0.81 mol). The only difference was that the transesterification took place at 180 ° C. for 60 minutes and at 200 ° C. for 60 minutes. The recovered polymer yield was about 63 g. T _g was about 89 ° C. and T _m was about 214 ° C. (second heating, 10 ° C.). ¹ H-NMR (HFIP-d) δ: 7.30 (m, 2H), 4.70-4.30 (m, 4H). M _n (SEC) about 16700D, PDI (SEC) 2.0. IV about 0.59 dL / g.

  The cut pellets thus obtained were polymerized in the solid state to increase the molecular weight. The pellet was heated under vacuum at 200 ° C. for 72 hours under vacuum, and the final IV was about 0.96 dL / g.

Stage 3B: Production of PEF film by compression molding Similar to the procedure described in Comparative Example A except that instead of 260 ° C for PET, the press was preheated to a target temperature of 250 ° C for PEF. Using the procedure, a compression molded film was produced from the PTF polymer produced in Step 1A.

  The compression molded PEF film was analyzed for permeation to the CM15 hydrocarbon fuel mixture and the results are shown in Table 1.

Example 4: Extruded poly (trimethylene-2,5-furandicarboxylate) (PTF) film used as a hydrocarbon fuel barrier layer Stage 4A: Preparation of PTF prepolymer by polycondensation of bioPDO ™ and FDME A 10 pound stainless steel stirred autoclave (Delaware valley steel 1955, vessel #: XS1963) with stir bar and condenser was added to 2,5-furandimethyl ester (2557 g), 1,3-propanediol (1902 g), titanium (IV) Isopropoxide (2 g) and Dovernox-10 (5.4 g) were charged. A nitrogen purge was applied and stirring was initiated at 30 rpm to form a slurry. With stirring, autoclave was applied to 3 cycles of pressurizing to 50 psi nitrogen followed by evacuation. A weak nitrogen purge (about 0.5 L / min) was then established and an inert atmosphere was maintained. While the autoclave was heated to a set point of 240 ° C, methanol evolution began at a batch temperature of 185 ° C. The methanol distillation lasted 120 minutes, during which time the batch temperature rose from 185 ° C to 238 ° C. When the temperature leveled off at 238 ° C., a second charge of titanium (IV) isopropoxide (2 g) was added. At this point, a vacuum ramp was initiated and in 60 minutes the pressure dropped from 760 torr to 300 torr (pumping through the column) and from 300 torr to 0.05 torr (pumping through the trap). At 0.05 torr, the mixture was placed under vacuum and under stirring for 5 hours, after which the vessel was pressurized to 760 torr using nitrogen.

The formed polymer was recovered by pumping the melt through an outlet valve at the bottom of the vessel into a quench water bath. The thus formed strand is passed through a pelletizer equipped with an air jet, the polymer is dried so as not to contain moisture, and the polymer strand is cut to have a length of about 1/4 inch and a diameter of about 1/8 inch. The chip was formed. The yield was about 2724 g (about 5 pounds). T _g was about 58 ° C. (DSC, 5 ° C./min, second heating), and T _m was about 176 ° C. (DSC, 5 ° C./min, second heating). ¹ H-NMR (TCE-d) δ: 7.05 (s, 2H), 4.40 (m, 4H), 2.15 (m, 2H). M _n (SEC) about 10300D, PDI 1.97. IV about 0.55 dL / g.

Step 4B: Production of high molecular weight PTF polymer by solid phase polymerization of the PTF prepolymer of step 4A To increase the molecular weight of the PTF prepolymer (described above), solid phase polymerization is performed using a heated nitrogen fluidized bed. It was. The quenched and pelletized PTF prepolymer was first crystallized by placing the material in an oven followed by heating the pellet to 120 ° C. for 240 minutes under a nitrogen purge. At this point, the oven temperature was raised to about 168 ° C. and the pellet was placed under nitrogen purge conditions to increase the molecular weight for a total of 96 hours. The oven was turned off and the pellets were cooled. The resulting pellet had an IV measurement of about 0.99 dL / g.

Step 4C: Production of PTF Film by Extrusion A 30 mm W & P (Werner & Phleiderer) twin screw extruder equipped with a 60/200 mesh filter screen and a 25 cm wide film casting die was used for film extrusion. PTF pellets were fed, the extruder barrel zone (11 total) and die were all set to 230 ° C, and the extruder feed temperature was set to 180 ° C. A vacuum hole in the barrel section 6 was used. The feed rate was 10 pounds / hour and the extruder screw speed was 125 rpm. The panel melting temperature was measured at 233 ° C. After casting on a cooling drum at a temperature set point of 40 ° C., the film was recovered and the measured film thickness was about 0.1 millimeters and the width was about 22 centimeters. Following the casting process, the produced film was cut into paper size film (about 20 × 30 centimeters) and used for further testing.

  Extruded PTF films were analyzed for permeation to the CE10 hydrocarbon fuel mixture and the results are shown in Table 2.

Example 5 Extruded Crystallized PTF Film Used as a Hydrocarbon Fuel Barrier Layer Stage 5A: Production of PTF Prepolymer by Biocondensation of bioPDO ™ and FDME 100 lbs equipped with stir bar, stirrer and condensation tower 2,5-furandimethyl ester (27000 g), 1,3-propanediol (20094 g), and titanium (IV) butoxide (40.8 g) were charged into a stainless steel stirred reactor. A nitrogen purge was applied and stirring was started at 51 rpm to form a slurry. While stirring, the reactor was purged with a weak nitrogen to maintain an inert atmosphere. While the autoclave was heated to the set point 243 ° C, methanol evolution began at a batch temperature of about 158 ° C. The methanol distillation lasted 265 minutes, during which time the batch temperature rose from 158 ° C to 244 ° C. After the methanol distillation was complete, a vacuum ramp was started and the pressure dropped from 760 torr to 1 torr in 120 minutes. At 1 Torr, the mixture was placed under vacuum and under stirring for 165 minutes to achieve a minimum pressure of 0.56 Torr, in addition to intermittent reduction in stirring speed, after which the vessel was 760 Torr using nitrogen. Pressurized again.

  The formed polymer was recovered by pumping the melt through an outlet valve at the bottom of the vessel into a quench water bath. The strand thus formed was passed through a pelletizer equipped with an air jet, the polymer was dried so as not to contain moisture, and the polymer strand was cut to form pellets. The yield was about 24710 g. IV about 0.63 dL / g.

Step 5B: Production of High Molecular Weight PTF Polymer by Solid Phase Polymerization of PTF Prepolymer In order to increase the molecular weight of the PTF prepolymer (described above), solid phase polymerization was performed using a rotating drum equipped with a heated nitrogen purge. . The quenched and pelletized PTF prepolymer was first crystallized and cooled by placing the material in a rotary dryer and subsequently heating the pellet to 110 ° C. for 240 minutes under a nitrogen purge. The crystallized pellets were screened to remove clumps and debris. The crystallized pellets were returned to the rotary dryer, the temperature was raised to about 165 ° C., the pellets were placed under nitrogen purge conditions and the molecular weight was increased for a total of 277 hours. The oven was turned off and the pellets were cooled. The resulting pellet had an IV measurement of about 1.005 dL / g.

Step 5C: Production of Crystallized PTF Film by Annealing A film was produced by extrusion using the PTF obtained from Step 5B in the same manner as in Step 4C of Example 4. The extruded PTF film was crystallized by annealing in a vacuum oven with a nitrogen sweep overnight at 110 ° C. The thickness of this film was 0.012 inches.

  Extruded crystallized PTF films were analyzed for permeation to the CM15 hydrocarbon fuel mixture and the results are shown in Table 1.

Comparative Example B Extruded EVOH Film Used as a Hydrocarbon Fuel Barrier Layer An ethylene vinyl alcohol EVOH film was extruded in the same manner as in Step 4C of Example 4. The thickness of this EVOH film was about 0.25 mm.

  Extruded EVOH films were analyzed for permeation through the M15 hydrocarbon fuel mixture and the results are shown in Table 1. Some variations are inherent in the measurement, and partly due to differences in sample thickness and quality.

  Furan-based polyesters, polyalkylene furandicarboxylates such as PTF, PBF and PEF are all generally superior to the CM15 fuel compared to the comparative EVOH, which is the most commonly used polymer hydrocarbon barrier It can be seen from Table 1 that a transmission barrier is shown. Accordingly, PTF, PBF and PEF are all suitable for use as hydrocarbon barrier layers in multilayer structures including one or more structural layers and one or more bonding layers.

  Of the three polyalkylene furandicarboxylates tested, it can also be seen from Table 1 that PTF has the best barrier to CM15 fuel and is nearly three orders of magnitude better than the EVOH monolayer tested. Furthermore, the barrier performance of PTF against CM15 fuel can be further improved by crystallization, as shown by the crystallized PTF (cPTF) of Example 5, which is similar to that of PTF (Example 1) and cPTF (Example 5). Both have a CM15 fuel permeation barrier superior to PET and EVOH.

  Since ethanol is a large molecule present in CE10 compared to methanol present in CM15, it can be seen from Table 2 that PBF has an excellent permeation barrier for CE10 compared to CM15 fuel. From these transmission data, PTF shows exceptional performance for fuel blend components: methanol, ethanol, isooctane and toluene.

Example 6: Three-layer laminated structure (PTF / Bynel / HDPE) used as a hydrocarbon fuel barrier layer
Production of three-layer laminate film in hot press Using the above polymer film production procedure, the PTF pellets and HDPE-PE pellets produced in Step 5B of Example 5 were pressed at 250 ° C. and 220 ° C., respectively, A 5-8 mil thick film (15 cm × 15 cm) was formed. A 2 mil thick Bynel 21E533 film (bonding layer) sheet was placed between the PTF film sheet and the HDPE film sheet. The resulting three-layer structure was placed between two PFA fluoropolymer release sheets to prevent sticking to the brass sheet and then placed on a warm brass sheet to form a three-layer sample. Excess air pockets were removed from the three-layer sample by pressing the sample with a squeegee followed by a hand roller. The three layer sample was then placed on a 240 ° C. preheated Pasadena press, heated on the platen for 60 seconds, and then exposed to a pressure of 40 psig for 30 seconds. The three layer sample was temporarily lowered for a few seconds and then pressed again at 40 psig for 30 seconds. A total of three press-release cycles were performed to minimize air bubbles in the three-layer laminate sample. The three layer laminate sample was removed from the press and placed between two cooling plates. The cooled three-layer laminated film was separated from the PFA release sheet and measured for its transmission. The thickness of the three layer structure was 0.017 inch.

  The laminate 3 layer structure with PTF as barrier layer and facing the fuel was analyzed for permeation to the CM15 hydrocarbon fuel mixture and the results are shown in Table 3.

Comparative Example C: 5-layer coextruded sheet structure used as a hydrocarbon fuel barrier layer (polypropylene / Bynel® / EVOH / Bynel® / polypropylene)
Five-layer sheets (width of about 600 mm and about 0.72 mm) were produced on the experimental commercial Sano 5-layer shared extrusion line. The nominal thickness distribution of the layer was 45 / 2.5 / 5 / 2.5 / 45 (by thickness%). The actual sample tested has a total thickness of about 0.72 millimeters and the EVOH layer has a thickness of about 0.025 millimeters. The four processing conditions of the extruder were set according to standard processing conditions recommended by various suppliers of the resins used and the die temperature was maintained at 230 ° C. The speed line varied from 5 to 8 m / min. The resin used included the homopolymer PP P4G3Z-050 (3.5 MI), Bynel® 50E662 in the tie layer and EVAL® J102 as the barrier layer.

Example 7: Co-extruded 5-layer structure used as a hydrocarbon fuel barrier layer-A / B / C / B / A (HDPE / Bynel / PTF / Bynel / HDPE)
Step 7A: Processing of the remaining PTF polymer from Step 1 PTF prepolymer that is not converted to pellets or out of pellet size specification by the process shown in Step 5A of Example 5 used to make the PTF prepolymer About 3 kg of residue was produced. This production was repeated 10 times or more. This residue includes pellets, uncut strands, solidification polymer recovered during the pelletization process and removal of the polymer melt from the reactor. The remainder recovered in each of the Stage 5A productions was combined and further upgraded to a more usable product. The solid part was frozen with liquid nitrogen and crushed into small pieces with a hammer. The entire remainder was then freeze-ground with a hammer mill to produce a mixture of powder and polymer particles. The crushed residual polymer was melt processed using a 30 mm twin screw extruder (ZSK30 from Coperion) operated at a barrel temperature of 230 ° C. and a mass throughput of 30 pounds / hour. The polymer melt was extruded through a single die into a quench water bath. The strand thus formed was passed through a pelletizer equipped with an air jet, the polymer was dried so as not to contain moisture, and the polymer strand was cut to form pellets. The residual yield processed was about 27100 g of pellets. IV about 0.63 dL / g.

SEC analysis showed that the polyester had _Mn (SEC) 13,120 Da and PDI2.2.

Step 7B: Production of high molecular weight PTF polymer by solid phase polymerization of PTF prepolymer residue To increase the molecular weight of PTF prepolymer residue, solid phase polymerization (SPP) was performed using a convection oven with N ₂ purge. . The quenched and pelletized residue was first crystallized by placing the material in a convection oven followed by heating the pellet to 110 ° C. for 240 minutes under a nitrogen purge and then cooling to room temperature. The crystallized pellets were screened to remove agglomerates and broken pellets. The crystallized and sieved pellets were returned to the convection oven, the temperature was raised to about 165 ° C. and the pellets were placed under a heated nitrogen purge to increase the molecular weight for a total of 168 hours. The oven was turned off and the pellets were cooled to room temperature. The resulting pellet had an IV measurement of about 1.06 dL / g.

Step 7C: Production of 5-layer film by coextrusion A 5-layer ABCBA film was produced by coextrusion. The A layer was manufactured from HDPE-S-N. B layer is a commercial bond such as Bynel® 21E533, Bynel® E418, Bynel® 22E999, Elvaloy® AS, Fusbond® N525 and Bynel® 41E754. Is a layer. Layer C was a barrier layer using the PTF obtained from Step 7B. Six different multilayer films were made using PTF as the barrier layer, including each of the B-bond layers shown. The proportion of the extruder was set to achieve a nominal value of 35% / 10% / 10% / 10% / 35% according to the volume distribution of the layers.

A layer was fed from the length / screw diameter (L / D) ratio 24/1 diameter 44 mm (1 _^3/4 inch) single screw extruder. The extruder was made by NRM. The screw speed was 25 RPM, and the temperature set points for barrel zones 1, 2, and 3 were 190 ° C, 200 ° C, and 230 ° C, respectively. The B layer was supplied from a single screw extruder of 25 mm (1 inch) diameter with an L / D ratio of 30/1. This extruder was from the Davis Standard Company. Except for the 5-layer structure with Bynel 41E754 as the tie layer with set points of 200 ° C., 210 ° C., 220 ° C., and 230 ° C., the screw speed is 31 RPM and the barrel zones 1, 2, 3, and 4 The set points were 190 ° C, 200 ° C, 210 and 220 ° C, respectively. C layer is supplied from the single screw extruder having a diameter of L / D ratio 30/1 32mm ^{(1 _1/4} inch). The extruder was from Wayne Machine and Die. The screw speed was 8 RPM relative to PTF, and the temperature set points for barrel sections 1, 2, 3, and 4 were 190 ° C, 200 ° C, 210 ° C, and 220 ° C, respectively. Three extruders fed into a 203 mm (8 inch) vane die equipped with an A-B-C-B-A switching plug. The blade die and changeover plug were sold by Cloeren Company. The die temperature was set at 230 ° C.

  The molten five layer coextrudate exiting the die was quenched between a 203 mm (8 inch) diameter chrome casting roll and a 127 mm (5 inch) diameter nip roll. The casting roll and nip roll were hollow for water cooling. The quenched and polished sheet was wound on a paper core having a diameter of 76 mm (3 inches). The casting and winding unit was from Killion-DavisStd. The sheet thickness was 0.69 to 0.76 mm.

  The adhesion between the barrier layer and the structural layer using the tie layer is demonstrated and summarized in Table 3.

  Although some are superior to others, all of the above-described tie layers tested provide good adhesion between the barrier layer and the structural layer in a multi-layer structure produced using covalent extrusion.

  The extruded 5-layer structure with PTF as the barrier layer was analyzed for permeation to the CM15 hydrocarbon fuel mixture and the results are summarized in Table 4.

From Table 4, it can be seen that the three-layer structure of PTF with Bynel as the bonding layer and HDPE as the structural layer shows an excellent transmission barrier compared to the five-layer structure with EVOH as the barrier layer. The three-layer structure is placed with the PTF facing the fuel. Since the transmittance calculation is for the total thickness of the multilayer sheet and HDPE and the bonding layer are not expected to contribute to the barrier of the structure, the total transmission of the three-layer structure of Example 6 with PTF as the barrier layer. The rate (0.2157 g-mm / m ² -day) is higher than the single layer PTF of Example 1 (0.0108 & 0.0122 g-mm / m ² -day).

Claims (15)

a. A hydrocarbon fuel permeation barrier layer comprising a furan-based polyester, wherein the furan-based polyester:
i. 2,5-furandicarboxylic acid or a derivative thereof,
ii. C ₂ -C ₁₂ aliphatic diol or polyol, and iii. Optionally, at least one of polyalkylene ether glycol (PAEG), polyfunctional acid or polyfunctional hydroxyl acid;
A hydrocarbon fuel permeation barrier layer derived from
b. A first structural layer comprising at least one of a polyolefin, polyester, or polyamide;
c. A first tie layer disposed between the barrier layer and the first structural layer, the first tie layer comprising an ethylene-based copolymer;
A multilayer structure comprising
A multilayer structure wherein the hydrocarbon fuel permeation barrier layer has a thickness in the range of 0.5 to 50% of the total thickness of the multilayer structure so as to provide a permeation barrier for hydrocarbon fuel.   The multilayer structure of claim 1, wherein the multilayer structure further comprises a second structure layer, wherein the barrier layer is disposed between the first bonding layer and the second structure layer.   A multilayer structure further comprising a second tie layer, wherein the barrier layer is disposed between the first tie layer and the second tie layer, and the first tie layer comprises an ethylene-based copolymer. Item 3. The multilayer structure according to Item 2.   The multilayer structure of claim 1 wherein the furan-based polyester is poly (trimethylene furandicarboxylate).   The barrier layer further comprises poly (trimethylene furandicarboxylate) (PTF) such that the furan-based polyester is different from PTF, and the furan-based polyester and PTF comprise the furan-based polyester and PTF. The multilayer structure of claim 1, wherein the multilayer structure forms a polymer blend comprising 0.1 to 99.9 wt% PTF, based on the total weight of the polymer blend composition.   The barrier layer further comprises poly (alkylene terephthalate) (PAT), and the furan-based polyester and PAT have a PAT of 0.1 to the total weight of the polymer blend comprising the furan-based polyester and PAT. The multilayer structure of claim 1 forming a polymer blend comprising 99.9 wt%.   The multilayer structure of claim 6, wherein the barrier layer comprises poly (trimethylene furandicarboxylate) (PTF) and poly (ethylene terephthalate) (PET).   The multi-layer structure according to claim 1, which takes the form of a housing with an inlet / outlet for introducing hydrocarbon fuel in a closed vessel defined by the housing.   The multi-layer structure according to claim 1, which takes the form of a hollow body selected from the group consisting of hoses, pipes, ducts, tubes, tube materials or conduits.   An article for storing or transporting hydrocarbon fuel, comprising a multilayer structure according to claim 1, in the form of a housing with an inlet / outlet for introducing hydrocarbon fuel in a closed vessel defined by the housing. An article wherein the multilayer structure provides a permeation barrier for the hydrocarbon fuel.   11. The article of claim 10, further comprising means for closing the doorway such that closing the doorway isolates the material from the external environment.   The article of claim 10, wherein the hydrocarbon fuel comprises one or more of ethanol, methanol, butanol, toluene, xylene, isooctane, gasoline, kerosene, liquefied petroleum, diesel and biodiesel.   The fuel container, a fuel container with a lid, a fuel container with a sealing part, a fuel can, a fuel valve, a fuel inlet, a fuel supply part, a fuel tank, and a fuel line. The article described. A method for reducing the permeation of hydrocarbon fuel through a fuel tank comprising providing a fuel tank having at least one polymer barrier layer, wherein the polymer barrier layer comprises a furan-based polyester, Polyester is:
a) 2,5-furandicarboxylic acid or a derivative thereof,
b) C ₂ ~C ₁₂ aliphatic diols or polyols,
c) optionally, at least one of polyalkylene ether glycol (PAEG), polyfunctional acid or polyfunctional hydroxyl acid,
Derived from the method. A method for storing or transporting hydrocarbon fuel, comprising providing a housing with an inlet and outlet for introducing hydrocarbon fuel in a closed vessel defined by the housing, the housing comprising furan-based polyester. The furan-based polyester is:
a) 2,5-furandicarboxylic acid or a derivative thereof,
b) C ₂ ~C ₁₂ aliphatic diols or polyols,
c) Optionally, at least one of polyalkylene ether glycol (PAEG), polyfunctional acid or polyfunctional hydroxyl acid,
Derived from the method.

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